Compositions of epoxysilane and reactive polymer with cure catalyst and methods of preparation

ABSTRACT

The present invention provides stable epoxy silane solutions and emulsions and methods for the preparation of stable epoxy-silane solutions and emulsions comprising: (I) a water insoluble or slightly soluble epoxysilane; (II) optionally, an emulsifier; (III) water; (IV) a water dispersible polymer containing a functional group with an active hydrogen; and (V) a catalyst. Also provided are two part systems such that an epoxysilane solution or emulsion comprising components (I)-(III) are combined and the components (IV) and (V) may be added upon use of components (I) to (III). Moreover, additional components, such as pH buffers may be added. Said compositions may be used for, among other things, coatings, adhesives and sealants. The water epoxy functional silane for use herein are of the general structure R 1   a  R 2   b  Si(OR 3 ) 4-a-b  where R 1  is an epoxy substituted alkyl or aralkyl group, where the alkyl may have from four to thirty carbon atoms, R 3  is an alkyl or alkoxy-substituted alkyl, aryl or aralkyl group having from one to ten carbon atoms, R 2  is an alkyl group or alkoxy substituted alkyl, aryl or aralkyl group having from one to ten carbon atoms, a is one to three, and b is zero to two, with the proviso that a+b is 1, 2, or 3. R 1 , R 2 , and R 3  group may be cyclic, branched or linear.

This application is a continuation-in-part of application Ser. No. 08/735,055, filed Nov. 7, 1996, U.S. Pat. No. 5,714,532 which is a continuation of application Ser. No. 08/420,389, filed Apr. 12, 1995, now abandoned.

BACKGROUND OF THE INVENTION

Conventional organic solvent based polymer compositions have become disfavored due to problems associated with environmental pollution, conservation of resources and providing a safe working environment. Instead, aqueous solution or dispersion type coating compositions have been proposed as alternatives. In particular, much attention has been paid to reactive polymer emulsions and dispersions because of the ease with which they provide improved properties such as water and solvent resistance.

The use of combinations of polymers, aqueous emulsions and dispersions (latices) and epoxy resins or compounds is well known in the art. For example, U.S. Pat. No. 4,049,869 to Long taught a composition including a high acid acrylic latex (5 to 20% by weight), a crosslinking agent (1 to 10%) and an ultraviolet absorber for use in preserving porous inorganic substrates. The crosslinking agent can include an epoxy resin.

Water-soluble silanes as additives in latex systems have also been disclosed in the prior art. For example, U.S. Pat. No. 5,017,632 to Bredow disclosed coating compositions for Portland cement or metal. The coating composition thereof can be mixed from a pair of storage stable components; a dry mix including a fine particle size filler, an epoxy resin and optionally, a coarse aggregate, and a wet mix including a polymer latex, an amine-functional epoxy curing agent, and a water-soluble epoxy- or amino-silane.

U.S. Pat. No. 5,100,955 to Pons disclosed coating and adhesive compositions based on aqueous dispersions of addition polymers of one or more olefinically unsaturated monomers, emulsion stabilizers and/or emulsifiers and a water-soluble epoxysilane. The water-soluble epoxysilane is added preferably after the polymerization of the addition polymer. The shelf life, however, of such compositions is only from two to three days.

EP Patent No. 401,496 to Hahn disclosed aqueous silicon-modified plastic dispersions as adhesives by epoxysilane-treatment of a dispersion of emulsion copolymers containing carboxylic acid, amide and sulfonic acid groups. Water soluble epoxysilanes of the formula R₁ R₂ R₃ R₄ Si are disclosed with R₁ =(cyclo)alkyl with reactive oxirane group; R₂ =(cyclo)alkoxy, (cyclo)alkyl, aryl or aralkyl; R₃, R₄ =(cyclo)alkoxy, or OH. However, the composition of the synthetic latex is specific. Furthermore, the neat epoxysilane is added directly to the polymer.

In addition to these coating technologies, emulsions of trialkoxysilanes have been previously reported used as waterproofing agents. For example, buffered aqueous silane emulsions are disclosed in U.S. Pat. Nos. 4,877,654 and 5,393,330. Alkylalkoxysilanes are also emulsified with nonionic and anionic emulsifiers for water repellency properties in U.S. Pat. No. 5,226,954.

SUMMARY OF THE INVENTION

The present invention provides shelf stable compositions comprised of epoxysilane, a water dispersible or emulsifiable organic polymer which contains a functional group with an active hydrogen, together with a catalyst for curing the composition.. The corresponding method of the present invention for the preparation of a shelf stable composition comprises combining an epoxysilane compound in water with the organic polymer which contains a functional group with an active hydrogen, and adding at any point a catalyst for curing the composition..

One embodiment of the present invention provides shelf stable compositions comprised of water-insoluble or slightly soluble epoxysilanes, emulsifier and a water dispersible or emulsifiable organic polymer which contains a functional group with an active hydrogen, together with a catalyst for curing the composition.. The method of the present invention for the preparation of such a shelf stable composition comprises: (a) dispersing a water insoluble or slightly soluble epoxysilane compound in an aqueous solution with emulsifier to yield an aqueous emulsion, and (b) adding the silane emulsion to a water dispersed or emulsified organic polymer which contains a functional group with an active hydrogen, and adding at any point a catalyst for curing the composition..

Another aspect of the present invention is to provide an article coated and cured with any of the aforementioned reactive, aqueous compositions.

The compositions of the present invention are stable for at least about six (6) months. Moreover, improved properties such as solvent resistance, adhesion, smoothness, hardness and mar resistance are achieved with compositions of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides stable epoxy silane containing compositions and methods for the preparation of stable epoxy-silane containing compositions comprising: (I) an epoxysilane, which can be a water soluble, water insoluble or slightly soluble epoxysilane; (II) optional emulsifier; (III) water; (IV) water dispersible or emulsified polymer containing a functional group with an active hydrogen; and (V) a catalyst for cure of the composition. Also provided are two part systems such that an epoxysilane emulsion comprising components (I)-(III) are combined and the components (IV) and (V) may be added upon use of components (I) to (III). Moreover, additional components, such as pH buffers may be added. Contemplated herein are also compositions for the preparation of the above compositions, namely the silane (I), the emulsifier (II), and the catalyst (V).

The present invention provides highly stable epoxysilane containing compositions that do not seed or gel during storage. Generally, they are stable for at least two to three weeks and more preferably two to three months. In fact, these compositions containing less than twenty weight percent epoxysilane last longer than six months of storage. This compares favorably with the prior art which taught silane/polymer compositions which would lose properties, such as adhesion, or even gel after two-three weeks.

The catalyst can be any that permits curing of the composition at lower temperatures, on the order of 150° F., than is the case with compositions not containing the catalyst. The presence of the catalyst provides the additional advantage that one can use relatively water-soluble epoxysilanes and catalysts, thus providing greater freedom of operation and permitting the user to avoid having to use an emulsifier where such a component is not desired.

The cured product exhibits very satisfactory to superior properties such as high resistance to chemicals and high resistance to stains.

(I) SILANES

The epoxy functional silanes useful herein are of the general structure R¹ _(a) R² _(b) Si(OR³)_(4-a-b) where R¹ is an epoxy substituted alkyl or aralkyl group, where the alkyl may have from four to thirty carbon atoms, R³ is an alkyl or alkoxy-substituted alkyl, aryl or aralkyl group having from one to ten carbon atoms, R² is an alkyl group or alkoxy substituted alkyl, aryl or aralkyl group having from one to ten carbon atoms, a is one to three, and b is zero to two, with the proviso that a+b is 1, 2, or 3. Each R group may be cyclic, branched or linear. Water insoluble or slightly soluble silanes useful in this invention include silanes with solubilities between 0.1 and 8.0 weight percent in water. Water insoluble epoxy silanes are preferred. However, water soluble silanes can be used although compositions made with such silanes may be less stable for extended periods of time, i.e., more than two to three days at ambient conditions.

The preferred epoxy functional silanes include: ##STR1## where: R is (CH₂)_(m), where m has a value of zero to six;

R² is an alkyl, alkoxy-substituted alkyl, aryl or aralkyl group, each of said groups having from one to ten carbon atoms;

R³ is an alkyl, alkoxy-substituted alkyl, aryl or aralkyl group, each of said groups having from one to ten carbon atoms;

R⁴, R⁵, R⁶ or R⁷ are each hydrogen or an alkyl group having from one to six carbon atoms;

R⁸ is an alkyl group having from one to four carbon atoms or aralkyl or aryl group having six to ten carbon atoms; ##STR2##

n has a value of zero, one or two;

c, d and e each have a value of zero or one; and

f has a value of zero, one or two.

More specifically, R² denotes a substituted or unsubstituted monovalent hydrocarbon group exemplified by alkyl groups (e.g., methyl, ethyl, isobutyl,, and octyl groups), alkenyl groups (e.g., vinyl and allyl groups), aryl groups (e.g., phenyl, tolyl and naphthyl groups), and aralkyl groups (e.g., benzyl and 2-phenylethyl groups), as well as those substituted groups obtained by the replacement of one or more of the carbon atoms in the above named hydrocarbon groups with various kinds of atoms and/or groups including sulfur and oxygen, and/or replacement of one or more of the hydrogen atoms in the above named hydrocarbon groups with various kinds of groups, including, but not limited to, halogen atoms, epoxy, methacryloxy, acryloxy, carboxyl, ester, cyano, and polyoxyalkylene groups.

R³ are alkyl, alkoxyalkyl, aryl or aralkyl radicals such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and cyclo radicals such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Illustrative of suitable branched chain hydrocarbon radicals for R² are alkyl radicals such as isopropyl, isobutyl, sec-butyl, isobutyl, sec-amyl, and 4-methyl-2-pentyl. Alkoxyalkyl groups may be exemplified by n-butoxy ethyl and methoxy propyl. Aryl groups may be exemplified by phenyl and aralkyl groups may be exemplified by benzyl or ethyl phenyl.

Water soluble epoxysilanes can be provided by formulating such that all R³ groups are methyl. Water dispersible epoxysilanes, which are of lesser water solubility, are charaterized in that the R³ groups contain two or more carbon atoms.

R⁴, R⁵, R⁶ or R⁷ are hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms exemplified by alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl groups), alkenyl groups (e.g., vinyl and allyl groups), and aryl groups (e.g., phenyl group). These hydrocarbon groups may be substituted by halogen atoms and functional groups, including cyano and epoxy, for a part or all of the hydrogen atoms therein.

Examples of epoxy functional silanes used in accordance with the present invention include, but are not limited to, those silanes described by Brison and Lefort in French Patent No. 1,526,231. Specific examples are 2-(3,4-epoxycyclohexyl) ethyltriethoxysilane, 4-(methyldiethoxysilyl)-1,2-epoxycyclohexane, 3-(3,4-epoxycyclohexyl)propyl tri(isobutoxy) silane, 3-(2,3-epoxybutoxy)propyltriethoxysilane, and [2.2.1] bicycloheptane 2,3-epoxy-5-(2-triethoxysilyl)ethyl.

The silane(s) is present at 0.1 to 30 percent by weight of the total composition [(I)-(V)]. The preferred concentration is about 0.1 to 10 percent of the weight of the total composition. In preparing the precursor epoxy silane emulsion, as defined by components (I)-(III), the silane(s) is present at 0.1 to 60 weight percent.

(II) EMULSIFIER (OPTIONAL)

The emulsifiers for use herein, when such a component is desired, include nonionic, anionic and cationic surfactants or mixtures of nonionic with anionic or cationic surfactants. Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of the anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkyl benzene sulfonate, alkyl phosphate, alkylallyl sulfate ester salt, and polyoxyethylene alkylphosphate ester. Examples of the cationic surfactants include quaternary ammonium salts such as long chain alkyl trimethylammonium salts, long chain alkyl benzyl dimethyl ammonium salts, and di(long chain alkyl) dimethyl ammonium salts. A further listing of surfactants useful in the present invention may be those described in 1994 McCutcheon's Vol. 2: Functional Materials, North American Edition (The Manufacturing Confectioner Publishing Co., Glen Rock) 1994, which is incorporated herein by reference.

The emulsifier(s) when used should be present in the range of 0.05 to 30 weight percent based on weight of the total composition of (I)-(V) and preferably 0.2 to 20 weight percent of the total composition. In precursor epoxysilane emulsions containing an emulsifier, the emulsifier should be present at 0.1 to 50 weight percent of the epoxy silane (I).

The appropriate HLB (hydrophilic-lipophilic balance) of the surfactants is chosen to correspond to the HLB of the specific epoxy silane being emulsified. The method for selecting the optimum HLB for a substance is well known to one skilled in the art and described in "The HLB System" by ICI Americas Inc.

Because the reactive polymer emulsion, as defined by components (II)-(IV), may be prepared prior to the addition of the precursor epoxy silane emulsion, emulsifiers of the type described above can be used in preparing these precursor compositions. Again, the emulsifiers are chosen so that the appropriate HLB is chosen to correspond to the HLB of the specific reactive polymer being emulsified with the proviso that the emulsifier(s) chosen to emulsify the reactive polymer are compatible with the emulsifier(s) used to make the precursor epoxysilane emulsion. In the precursor reactive polymer emulsion, the emulsifier should be present at 1 to 50 weight percent of the reactive polymer.

(III) WATER

The water may be present in an amount ranging from 29.85 to 99.75 weight percent of the total composition (I)-(IV). When a precursor silane emulsion is made without the polymer, about 39 to 99.75% water should be present.

(IV) POLYMERS

The reactive polymers of the present invention are those which have an active hydrogen thereon, preferably in the form of a carboxylic group. Exemplary of such polymers are those which contain terminal or pendant carboxyl groups (--COOH), some of which may be in its neutralized salt form (e.g., --COOK). These reactive polymers have molecular weights between 500 and 10⁸ gms/mole. The preferred reactive polymer contains a carboxylic acid group in an amount sufficient to have an acid number, as determined by ASTM D669, between 1 and 780, and preferably, between, 10 and 280. The polymers may be added as dispersions, with no emulsifier, or as emulsions, with emulsifiers therein.

Examples of reactive polymers which can be used in the present invention include carboxylic acid modified polymers chosen from the following: polyethylene, polypropylene, polyethylene propylene copolymer, urethanes, epoxies, polystyrenes and urethane acrylic polymers. Also useful herein are acrylic homopolymers, vinyl acrylic polymers, methacrylic polymers, styrene acrylic copolymers, and polyesters. These reactive polymers may also contain other organic functional groups, including hydroxyl, amide, vinyl and halogens are contemplated as being within the scope of reactive polymers.

Specific examples of preferred reactive polymers which can be used in accordance with this invention include commercially available styrene acrylic emulsion polymers, such as JONCRYL®s 554, 540,77, and 95, and SCX 2500, all commercially available from SC Johnson Polymer of Racine, Wis. Other specific examples of commercially available preferred reactive polymers materials which can be used include NEOCRYL® acrylic emulsions, NEOREZ® water-borne urethane polymers and NEOPAC® water-borne urethane acrylic copolymers, available from ZENECA Resins of Wilmington, Mass., and UCAR® acrylic and vinyl acrylic latexes available from Union Carbide Corporation of Danbury, Conn.

Polymer dispersions, which contain no emulsifiers, may also be used herein.

The polymer should be present at 0.1 to 70 weight percent of the total composition.

(V) CATALYST

The compositions of the present invention should contain a catalyst component, composed of one or more than one catalyst capable of enabling the composition to cure faster at ambient or elevated temperatures compared to the same composition without the catalyst.

Several types of compounds are useful in this regard. Examples of types of useful compounds include amines, organotin compounds, organoammonium halides, and organophosphonium halides.

Useful amine compounds include:

heterocyclic amines, preferably imidazoles but also including piperazines, pyridines, and pyrrolidines, and including heterocyclic amines which are unsubstituted or substituted with one or more alkyl groups containing 1 to 6 carbon atoms, or with one or more silyl-C₁ -C₄ -alkyl groups wherein the silyl atom is substituted with a total of three substituents selected from the group consisting of alkyl and alkoxy groups containing 1 to 6 carbon atoms; preferred examples of catalysts of this type include 2-ethyl-4-methyl-1H-imidazole and 1-[3-(trimethoxysilyl)propyl}-1H-imidazole;

tertiary amines, wherein the nitrogen atom is substituted with a total of three substituents selected from the group consisting of alkyl containing 1 to 6 carbon atoms, unsubstituted benzyl, and benzyl substituted with one or more of alkyl containing 1 to 6 carbon atoms, hydroxyl, and dialkylaminoalkylene wherein each alkyl group contains 1 to 6 carbon atoms and the alkylene bridge contains 1 to 6 carbon atoms (preferred examples of this type of amine catalyst including N-benzyl-N-dimethylamine, and tris-2,4,6-(dimethylaminomethyl)phenol);

polyamides; and

polyalkylene polyamines, corresponding to the formula H₂ N-(ALK-NH)_(i) -H wherein i is 1 to 10 and preferably 2-4, and each ALK is C₂ H₄, C₃ H₆, or C₄ H₈ and preferably C₂ H₄ (a preferred example of this type of amine catalyst being tetraethylenepentamine).

Useful organotin compounds include mercaptoalcohol, mercaptide or sulfide forms of diorganotin having a Sn--S or Sn═S bond. Further, illustrative examples are R₂ Sn(SCOO) type compounds, such as (n-C₄ H₉)₂ Sn(SCH₂ COO); R₂ Sn(SS) type compounds, such as (n-C₈ H₁₇)₂ Sn(SCH₂ COOCH₂ CH₂ OCOCH₂ S); R₂ Sn(SCH₂ COOR)₂ type compounds, such as (n-C₄ H₉)₂ Sn(SCH₂ COOC₈ H₁₇ -iso)₂ ; RSn(SCH₂ COOR)₃ type compounds, such as (n-C₄ H₉)Sn(SCH₂ COOC₈ H₁₇ -iso)₃ ; R₂ Sn═S compounds, such as (n-C₈ H₁₇)₂ Sn═S or the like; and ##STR3## where R⁵ =1-8 carbon atoms alkyl or aryl; W=--S-- or --O--; and Z=--CH₂ CH(CH₂ OH)-- or --CH₂ CH(OH)CH₂ --. Preferred examples are FOMREZ UL-1, UL-22, and UL-32 from Witco and dibutyltin bis(1-thioglycerol), dibutyltin oxide and dibutyltin ditnercaptide.

Useful organoammonium halides and organophosphonium halides are Lewis acids corresponding respectively to the structures (A¹)(A²)(A³)N-halide and (A¹)(A²)(A³)(A⁴)P-halide wherein A¹, A², A³ and A⁴ are independently alkyl containing 1 to 4 carbon atoms, benzyl, or phenyl, and halide is chloride or bromide. The ammonium compounds are preferably substituted with at most one benzyl or phenyl group, whereas the phosphonium compounds can be substituted with 0 to 3 benzyl or phenyl groups. Preferred examples are benzyltrimethylammonium chloride and butyl- (or ethyl-)triphenylphosphonium bromide.

The compositions of the present invention optionally may comprise other water soluble/emulsifiable/dispersible curing catalysts, which are hydrolytically stable, to modulate the curing conditions. Examples of such catalysts are organotitanate, organotin, chelated titanium, aluminum and zirconium compounds, and combinations thereof. Examples of chelated titanates are dihydroxy bis [2-hydroxypropanato (2-)-O¹,O₂ ] (2-) titanate, mixed titanium ortho ester complexes, acetylacetonate chelate, bis(ethyl-3-oxobutanolato-O¹,O³ ] bis(2-propanolato) titanium, isopropoxy(triethanolaminato) titanium and alkanolamine complex of titanium. Examples of organotin catalysts are FOMREZ® UL-1, UL-22, and UL-32 from Witco of Greenwich, Conn. and dibutyltin bis(1-thioglycerol).

The catalyst can be used in an amount of 0.01 to 20 percent, preferably 0.1 to 10 parts, based on reactive polymer component (IV).

(VI) OPTIONAL INGREDIENTS

The composition of the present invention may additionally: contain cross-linking agents, such as urea and melamine resins which are methylolated and/or alkoxylated, epoxy resins, aziridines and carbodiimides. Such agents may be present at 0.1 to 20 weight percent of the total composition, as long as they do not destabilize the composition during storage.

The pH of the total composition may impact upon its hydrostability. High alkalinity or high acidity of the composition catalyzes the hydrolysis and condensation of the alkoxysilyl group of the epoxy silane. The closer the pH of the composition is to neutral (pH=7), the better the stability of the emulsion. Therefore, the preferred range of pH of the total composition is 5.5 to 8.5. Substances which can be used to adjust the pH are organic or inorganic buffers including sodium acetate, sodium citrate, sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate, sodium dihydrogen phosphate, and the corresponding potassium salts.

Other optional ingredients for inclusion herein are fillers, thixotropes, pigments, plasticizers, coalescing agents, biocides and fungicides as are commonly known and used in the art.

METHOD OF PREPARATION AND USE

The precursor epoxysilane compositions of the present invention are prepared by first mixing the epoxy functional silane (I) with water. If desired, an emulsifier (II) is added and the mixture is stirred to provide a white, milky emulsion. The pH of the resulting aqueous solution or emulsion is adjusted, if necessary, to pH 7.0±1.5.

The precursor epoxysilane solution or emulsion is added to the reactive polymer (IV) or to a reactive polymer emulsion [Components (II)-(IV)] to provide a stable composition. The method employed to mix these components is not critical and any commonly used low shear equipment, such as a blade or paddle mixer, is suitable. The catalyst (V) and any optional ingredients (VI) may be added at any time, although in some cases catalysts should be added last.

The solutions and emulsions may be used as two component systems, i.e., components (I)-(III) and components (IV)-(V), mixed in shortly before use, but have sufficient stability when mixed to be used as one-component systems. The composition of components (I)-(V) form uniform aqueous solutions, dispersions or emulsions. Many uses of these compositions require drying under ambient conditions or at moderately elevated temperatures (e.g., baking). The resulting dried material has excellent solvent resistance, chemical resistance, hardness, mar resistance, adhesion, water resistance, durability or weatherability.

The compositions made according to the present invention may be used as industrial and architectural coatings, sealants, wood coating, adhesives and in mastics, i.e., generally in any application where the polymer would be used. For example, in textile print paste applications, the composition of the present invention would provide crock resistant colorfast applications. In wood coating, the present compositions would provide stain resistance, mar resistance and block resistance between latex surfaces in storage. As to architectural coatings, the present composition would provide scrub resistance and other improved properties. In sealants, the present composition would provide adhesion to inorganic surfaces. As is clear to one of ordinary skill in the art, there is vast array of applications of the present invention in coating, sealant, adhesives, masonry sealers, fiberglass binders and sizes, inks and other water-borne polymer systems.

EXAMPLES

1. Preparation of a 40% β 3,4-epoxycyclohexyl) ethyltriethoxysilane (Silane A) emulsion with 5% surfactants--Into a beaker were added 3.85 grams of SPAN® 60 surfactant (ICI Americas) and 3.65 grams of TWEEN® 40 surfactant (ICI Americas) which were heated together in a hot water bath to melt the solid materials. 60.0 grams of Silane A were added and the mixture was stirred with a mechanical stirrer. 82.5 grams of water were added and the mixture was stirred vigorously for approximately five minutes to provide a white, stable emulsion containing 40% by weight of Silane A.

2. Preparation of a 20% Silane A emulsion with 5% surfactants--Into a beaker were added 3.5 grams of SPAN® 60 and 1.5 grams of TWEEN® 40 which were mixed and heated together in a hot water bath to melt the solid materials. 20.0 grams of Silane A were added and the mixture was stirred with a mechanical stirrer. 75.0 grams of water were added and the mixture was stirred vigorously for approximately five minutes to provide a white, stable emulsion containing 20% by weight of Silane A.

3. Preparation of a 40% Silane A emulsion with 8% surfactants--Into a beaker was added 2.18 grams of SPAN® 80 surfactant (ICI America) and 2.22 grams of TWEEN® 40 which were mixed together. To the surfactant mixture was added 22.0 grams of Silane A and the mixture was stirred with a mechanical stirrer. 28.6 grams of water were added and the mixture was stirred vigorously for approximately five minutes to provide a white, stable emulsion containing 40% by weight of Silane A.

4. Preparation of a 40% Silane A emulsion with 10% surfactants--Into a beaker was added 2.73 grams of SPAN® 80 and 2.77 grams of TWEEN® 40 which were mixed together. To the surfactant mixture was added 22.0 grams of Silane A and the mixture was stirred with a mechanical stirrer. 27.5 grams of water were added and the mixture was stirred vigorously for approximately five minutes to provide a white emulsion containing 40% by weight of Silane A.

5. Preparation of a 40% γ-glycidoxyropylmethyldiethoxysilane (Silane B) emulsion with 8% surfactants--1.93 grams of SPAN® 60 surfactant (ICI Americas) and 2.87 grams of Myrj® 52S surfactant (ICI Americas) were mixed together in a beaker and heated together in a hot water bath in order to melt the solid materials. 24.0 grams of Silane B were added and the mixture was stirred with a mechanical stirrer. 31.2 grams of water were added and the mixture was stirred for approximately thirty minutes to provide a white emulsion containing 40% by weight of Silane B. The epoxy silane emulsion was metastable and gelled within one month.

6. Preparation of 40% of γ-glycidoxypropyltri-(isobutoxy) silane (Silane D) with 6 weight percent surfactants--2.72 grams of SPAN® 60 surfactant and 1.18 grams of TWEEN® 40 were mixed together in a beaker and heated together in a hot water bath to melt the solid materials. 26.0 grams of D were added and the mixture was stirred with a Barhart Mixer for 20 minutes. 35.1 grams of water were added and the mixture was stirred for approximately thirty minutes to provide a white, stable emulsion containing 40% by weight of Silane D.

7. Preparation of 40% β-(3,4-epoxycyclohexyl)ethyl tri-(isobutoxy) silane (Silane E) emulsion with 6% surfactant--2.36 gms of SPAN® 60 and 1.04 grams of TWEEN® 40 were mixed together in a beaker and heated together in a hot water bath to melt the solid material. 26.0 grams of Silane E were added and the mixture was stirred with a mechanical stirrer for 10 minutes. 35.1 grams of water were added and the mixture was stirred for approximately ten minutes. Giv-Gard DXN (Givaudan-Roure), a preservative, was added.

8-33. Preparation of stable epoxy silane containing compositions--Stable epoxy silane containing compositions were prepared by adding various amounts of precursor epoxy silane emulsion (i.e., Components I-III), as prepared according to procedures described in Examples 1-7 to varying amounts of acid modified polymer dispersions (Components III-IV) or emulsions (Components II-IV). The mixtures of precursor epoxy silane emulsions and acid modified polymer dispersions or emulsions were stirred for approximately 10 minutes. The descriptions and amounts of each component of stable epoxy silane compositions are reported in Table I. Comparative Examples I-XLIV--Comparative examples of epoxy silane acid modified polymer dispersions or emulsions were prepared by mixing various amounts of the epoxy silanes A-E and Z with varying amounts of commercially available acid modified polymer dispersions or emulsions. (see Table 1 for definition of silanes). The comparative example of alkylsilane U-W and diepoxy resin X were prepared by making an emulsion of the alkylsilanes or diepoxy resins according to procedures similar to those described in Examples 1-7, and then mixing various amounts of these alkyl silanes or diepoxy resin emulsions with varying amounts of commercially available acid modified polymer dispersions or emulsions. For example, the precursor diepoxy resin emulsion was prepared by charging into a beaker 2.44 grams of SPAN® 60 and 0.91 grams of MYRJ® 52S. The solids were melted by heating in a warm water bath with stirring. 18.2 grams of water were added to the mixture and stirred vigorously. 3.5 grams of 3,4 epoxycyclohexylmethyl 3,4 epoxycyclohexylcarboxylate (Union Carbide ERL-4221) were added and the mixture was stirred vigorously to yield a viscous paste. 28.7 grams of water were added and the stirring was continued for fifteen minutes to yield a white emulsion. The descriptions and amounts of each comparative example is reported in Table I.

                                      TABLE I                                      __________________________________________________________________________     Compositions of present invention (precursor epoxy emulsions and                 carboxylic acid modified polymers) and comparative examples.                 __________________________________________________________________________     Example No.                                                                          Silane                                                                              %   Surfactant.sup.1                                                                      %  Polymer.sup.2                                                                           %  Water %                                   __________________________________________________________________________        8 A  0.198 SPAN 60 0.035 JONCRYL 554 46.53 53.22                                 TWEEN 40 0.015 (Acid No. 54)                                                 9 A  0.497 SPAN 60 0.087 JONCRYL 554 45.83 53.55                                 TWEEN 40 0.037                                                              10 A  0.998 SPAN 60 0.175 JONCRYL 554 44.66 54.09                                 TWEEN 40 0.075                                                              11 A  2.00 SPAN60 0.192 JONCRYL 554 44.65 52.97                                   TWEEN 40 0.182                                                              12 A  5.035 SPAN 60 0.485 JONCRYL 554 41.08 52.94                                 TWEEN 40 0.459                                                              13 A  0.497 SPAN 60 0.087 JONCRYL 540 42.91 56.47                                 TWEEN 40 0.037 (Acid No. 49)                                                14 A  0.998 SPAN 60 0.175 JONCRYL 540 41.81 56.94                                 TWEEN 40 0.075                                                              15 A  5.035 SPAN 60 0.485 JONCRYL 540 38.46 55.56                                 TWEEN 40 0.459                                                              16 A  2.00 SPAN 60 0.192 JONCRYL 77 45.00 54.46                                   TWEEN 40 0.182 (Acid No. 55)                                                17 B  2.00 SPAN 60 0.161 JONCRYL 77 43.70 53.90                                   MYRJ 52S 0.239                                                              18 A  2.00 SPAN 60 0.197 JONCRYL 95 28.50 69.12                                   TWEEN 40 0.182                                                              19 B  2.00 SPAN 60 0.161 JONCRYL 95 28.5 69.10                                    MYRJ 52S 0.239                                                              20 A  0.507 SPAN 60 0.089 SCX 2500 41.91 57.09                                    TWEEN 40 0.038 (Acid No. 19)                                                21 A  1.013 SPAN 60 0.172 SCX 2500 40.82 57.92                                    TWEEN 40 0.076                                                              22 A  5.045 SPAN60 0.486 SCX 2500 37.58 56.43                                     TWEEN 40 0.460                                                              23 A  5.035 SPAN 60 0.485 JONCRYL 624 42.83 51.19                                 TWEEN 40 0.459 (Acid No. 50)                                                24 A  5.035 SPAN 60 0.485 NEOREZ R-972 29.72 64.30                                TWEEN 40 0.459 (Acid No. 13)                                                25 A  5.035 SPAN 60 0.485 NEOREZ R-9679 32.34 61.68                               TWEEN 40 0.459 (Acid No. 23)                                                26 A  5.035 SPAN 60 0.485 UCAR Latex 100 54.20 39.83                              TWEEN 40 0.459 (Acid No. 13)                                                27 A 10.00 SPAN 60 1.203 UCAR Latex 100 47.24 40.42                               TWEEN 40 1.141                                                              28 A  5.035 SPAN 60 0.485 UCAR Latex 154 52.45 41.57                              TWEEN 40 0.459 (Acid No. 16)                                                29 A 10.00 SPAN 60 1.203 UCAR Latex 154 45.71 41.95                               TWEEN 40 1.141                                                              30 A  5.035 SPAN 60 0.485 UCAR Latex 163 50.70 43.32                              TWEEN 40 0.459 (Acid No. 15)                                                31 A 10.00 SPAN 60 1.203 UCAR Latex 163 44.19 43.47                               TWEEN 40 1.141                                                              32 B  2.00 SPAN 60 0.160 JONCRYL 77 43.7 53.90                                    MYRJ 52S 0.239                                                              33 B  2.00 SPAN 60 0.160 JONCRYL 95 28.50 69.10                                   MYRJ 52S 0.239                                                            __________________________________________________________________________     Comparative                                                                      Example Additive % Surfactant % Polymer % Water %                            __________________________________________________________________________       I NONE  NONE  JONCRYL 554 47.00 53.00                                          II NONE  NONE  SCX 2500 43.00 57.00                                            III NONE  NONE  JONCRYL 77 46.00 54.00                                         IV NONE  NONE  JONCRYL 540 44.00 56.00                                         V NONE  NONE  JONCRYL 95 30.00 70.00                                           VI X  2.00 SPAN 60 0.146 JONCRYL 540 43.12 54.63                                  MYRJ 52S 0.104                                                              VII X  2.00 NONE  JONCRYL 77 44.83 53.17                                       VIII A  2.00 NONE  JONCRYL 77 44.83 53.17                                      IX Y  2.00 NONE  JONCRYL 77 44.83 53.17                                        X C  2.00 NONE  JONCRYL 77 44.83 53.17                                         XI B  2.00 NONE  JONCRYL 77 44.83 53.17                                        XII Z  2.00 NONE  JONCRYL 77 44.83 53.17                                       XIII U  2.00 ARQUAD 2C75 0.100 JONCRYL 77 43.70 54.10                             ARMEEN DMCD 0.100                                                           XIV V  2.00 SPAN 60 0.206 JONCRYL 77 43.70 53.90                                  TWEEN 40 0.194                                                              XV W  2.00 SPAN 60 0.206 JONCRYL 77 43.77 53.90                                   TWEEN 40 0.194                                                              XVI Y  2.00 NONE  JONCRYL 95 29.40 68.60                                       XVII C  2.00 NONE  JONCRYL 95 29.40 68.60                                      XVIII B  2.00 NONE  JONCRYL 95 29.40 68.60                                     XIX X  2.00 NONE  JONCRYL 95 29.40 68.60                                       XX Z  2.00 NONE  JONCRYL 95 29.40 68.60                                        XXI X  2.00 SPAN 60 0.136 JONCRYL 95 28.50 69.26                                  MYRJ 525 0.104                                                              XXII A  2.00 NONE  JONCRYL 95 29.40 68.60                                      XXIII U  2.00 ARQUAD 2C75 0.100 JONCRYL 95 28.50 69.20                            ARMEEN DMCD 0.100                                                           XXIV V  2.00 SPAN 60 0.206 JONCRYL 95 28.50 69.10                                 TWEEN 40 0.194                                                              XXV W  2.00 SPAN 60 0.206 JONCRYL 95 28.50 69.10                                  TWEEN 40 0.194                                                              XXVI A  5.00 NONE  JONCRYL 624 46.55 48.45                                     XXVII Y  5.00 NONE  JONCRYL 624 45.55 48.45                                    XXVIII A  5.00 NONE  NEOREZ R-972 32.30 62.70                                  XXIX Y  5.00 NONE  NEOREZ R-972 32.30 62.70                                    XXX A  5.00 NONE  NEOREZ R-9679 35.15 59.85                                    XXXI Y  5.00 NONE  NEOREZ R-9679 35.15 59.85                                   XXXII A  5.00 NONE  UCAR Latex 100 58.90 36.10                                 XXXIII A 10.00 NONE  UCAR Latex 100 55.80 34.20                                XXXIV Y  5.00 NONE  UCAR Latex 100 58.90 36.10                                 XXXV Y 10.00 NONE  UCAR Latex 100 55.80 34.20                                  XXXVI A  5.00 NONE  UCAR Latex 154 57.00 38.00                                 XXXVII A 10.00 NONE  UCAR Latex 154 54.00 36.00                                XXXVIII Y  5.00 NONE  UCAR Latex 154 51.00 38.00                               XXXIX Y 10.00 NONE  UCAR Latex 154 54.00 36.00                                 XL A  5.00 NONE  UCAR Latex 163 55.10 39.90                                    XLI A 10.00 NONE  UCAR Latex 163 52.20 37.80                                   XLII Y  5.00 NONE  UCAR Latex 163 55.10 39.90                                  XLIII Y 10.00 NONE  UCAR Latex 163 52.20 37.80                                 XLIV X  1.00 SPAN 60 0.073 JONCRYL 540 43.05 55.82                                MYRJ 52S 0.051                                                            __________________________________________________________________________      A = (3,4epoxycyclohexyl)ethyltriethoxysilane                                   B = 3glycidoxypropyldiethoxymethylsilane                                       C = 3glycidoxypropyltriethoxysilane                                            D = 3glycidoxypropyltri-(isobutoxy)silane                                      E = (3,4epoxycyclohexyl)ethyltri-(isobutoxy)silane                             U = octyltriethoxysilane                                                       V = 1triethoxysilyl-2-methyldiethoxysilylethane                                W = amyltriethoxysilane                                                        X = (3,4epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate                   Z = 3glycidoxypropyltrimethoxysilane                                           .sup.1 does not include the surfactants that may be in commercial acid         modified polymer emulsion                                                      .sup.2 polymer weight is based upon solids in commercial products.       

34-84. Shelf Life Stability--The shelf life stability of the stable epoxy silane emulsions containing acid modified polymer dispersions or emulsions containing acid modified polymer dispersions or emulsions (Components I-IV) and the comparative examples were determined by measuring the viscosity of these compositions at various times after preparation. The viscosity was visually monitored for flow properties by titling a bottle containing the compositions back and forth or by measuring the viscosity of the compositions at 25° C. using a Brookfield viscometer. The stabilities of the compositions are reported in Table II.

These examples show that the stable epoxy emulsions containing acid modified polymers (Components I-IV) are shelf stable for a period greater than 12 weeks provided that the pH of the composition is relatively neutral. For example, Example 27 has 10 weight percent Silane A and UCAR latex 100 and at a pH=6, had a viscosity of 1300 cP after storing at room temperature for 12 weeks. The compositions of comparative examples XXXIII and XXXV, where 10 percent of the Silane A was simply mixed with UCAR latex 100 showed an increase in viscosity, as shown in Examples 38 and 39, respectively. Comparative example XXXIII had an increase in viscosity to 3000 cP after storing at room temperature for 12 weeks. Comparative example XXXV gelled within 12 weeks.

The shelf life of the stable epoxy emulsions is important to the end use properties. For example, compositions described in Example 24 were stable for a period of 12 weeks and form a film with a smooth surface upon drying as shown in Example 67. Comparative Example XXVIII, although it did not show a change in viscosity after 12 weeks, produced a poor quality film, as shown in Example 68. This film had a cracked surface and fish eyes. The source of the surface defects was attributed to the hydrolysis and condensation of the epoxy silane to form microgels and oils.

The pH of the compositions can have a pronounced effect on the stability of the compositions. For example, the viscosity of compositions set forth by Example 22 gradually increased and finally gelled after 24 weeks, as shown in Example 75. The increase in viscosity was attributed to the alkalinity of the composition. The pH of the composition was 8.6. These compositions may be useful as a two-component system where long pot time is required.

The stability of Example 32 was observed to be poor, as shown in Example 53. Silane B is slightly soluble in water and the water solubility of this silane makes the preparation of a stable precursor epoxy emulsion difficult. The precursor epoxy silane emulsion described in Example 3 gelled within one month. Lowering the water solubility of Silane B by changing the alkoxy groups attached to the silicon atom can significantly improve the stability of the precursor epoxy silane emulsion. For example, the precursor silane emulsion described in Example 6 was stable. Of note, Silane D is insoluble in water.

                                      TABLE II                                     __________________________________________________________________________     Data showing that the compositions of present invention (I-IV) form more       stable mixtures                                                                  than simple addition of epoxy silane or additive to aqueous emulsion or      dispersion of an                                                                acid modified polymers and produce good film quality. The table also          shows the effect of pH                                                           on the stability of the compositions of the present invention.                               Viscosity of mixture (visual observation or                      measured viscosity in cP at 25° C.) after                               storage at room temperature for various periods                                of time (weeks)                                                              Example No                                                                           Cmpstn                                                                              pH level                                                                            0   1  2  4      12 24 Film Quality                            __________________________________________________________________________     34    26   6.0  Thin   Thin                                                      35 XXXII 6.0 Thin  Thick                                                       36 XXXIV 6.0 Thin  Thick                                                       37 27 6.0 Thin    1300                                                         38 XXXIII 6.0 Thin    3000                                                     39 XXXV 6.0 Thin    gel                                                        40 28 4.0 Thin  Thin                                                           41 XXXVI 4.0 Thin  Thick                                                       42 XXXVIII 4.0 Thin  Thick                                                     43 29 4.0 Thin    1100                                                         44 XXXVII 4.0 Thin    1700                                                     45 XXXIX 4.0 Thin    2000                                                      46 30 4.0 Thin  Thin                                                           47 XL 4.0 Thin  Thick                                                          48 XLII 4.0 Thin  Thick                                                        49 31 4.0 Thin    1000                                                         50 XLI 4.0 Thin    1300                                                        51 XLIII 4.0 Thin    1500                                                      52 16 8.5 Thin  Thin    Smooth surface                                         53 32 8.5 Thin  Gel    Smooth surface                                          54 IX 8.5 Thin  Thin    Smooth surface                                         55 X 8.5 Thin Gel     Smooth Surface                                           56 XI 8.5 Thin  Gel    Smooth Surface                                          57 VI 8.5 Thin   Gel   Smooth Surface                                          58 18 8.5 Thin   Thin   Smooth Surface                                         59 33 8.5 Thin   Separate into   Smooth Surface                                      2 layers                                                                 60 XVI 8.5 Thin   Thin   Cratered Surface                                      61 XVII 8.5 Thin   Thin   Smooth Surface                                       62 XVIII 8.5 Thin   Thin   Cratered Surface                                    63 XXI 8.5 Thin   Separated into   Smooth surface                                    2 layers                                                                 64 23 8.0 Thin   Thick   Smooth surface                                        65 XXVI 8.0 Thin  Gel    Gel particles &                                                cratered                                                              66 XXVII 8.0 Thin   Thick   Rough, cratered                                             surface                                                               67 24 8.0 Thin   Thin   Smooth Surface                                         68 XXVIII 8.0 Thin   Thin   Fish eyes, cracked                                          surface                                                               69 XXIX 8.0 Thin   Thin   Cratered surface                                     70 25 8.0 Thin   Thin   Smooth surface                                         71 XXX 8.0 Thin   Thin   Fish eyes                                             72 XXXI 8.0 Thin   Thick   Fish eyes                                           73 20 8.5  50  49  50    63                                                    74 21 8.5  65  62  64    75                                                    75 22 8.6 148 146  107   gel                                                   76 II 8.5  28  30  29    45                                                    77 13 8.6  28  30  29   400                                                    78 14 8.6 135 154  192   440                                                   79 15 8.6 149 260  913   gel                                                   80 IV 8.6 228 206  208   240                                                   81  9 8.4 924 396  493   260                                                   82 10 8.5 234 378  500   930                                                   83 12 8.5 193 860 5675   gel                                                   84 I 8.5  4.13 397  423   520                                                __________________________________________________________________________

85-111. Solvent Resistance--The stable epoxy silane emulsions containing acid modified polymers are useful in improving the solvent resistance of films cast from them. The solvent resistance was determined by methyl ethyl ketone (MEK) double rubs. The tests were conducted according to ASTM D4752-87. Films were cured at 23° C. and 50% relative humidity for seven days or cured at 121° C. for 20 minutes and then 23° C. at 50% relative humidity for 7 days. The results of solvent resistance is reported in Table III.

The solvent resistance of films cast from compositions of the present invention was significantly better than films cast from the acid modified polymers alone. For example, the number of MEK double rubs of a film cast from compositions described in Example 16 and shown in Example 90 and cured at 121° C. for 20 minutes was 130 rubs. Comparative Example III, a film of JONCRYL 77 withstood only 11 MEK rubs, as shown in Example 91. Simple mixtures of Silane A and JONCRYL 77, Comparative Example VIII, withstood only 34 rubs. In some cases, simple blends of epoxy silanes and polymers, such as Comparative Example XI, yield solvent resistant films shown in Example 94, but the shelf life of these compositions is poor. For example, Comparative Example XI gelled in two weeks, as shown in Example 56/

                  TABLE III                                                        ______________________________________                                         Data showing that the compositions of present                                    invention have improved solvent resistance, as                                 demonstrated by MEK double rubs                                                         MEK double rubs                                                                    Cured at 23° C. at                                                                    Cured at 121° C.                             Example Compo- 50% relative humidity for 20 min and then at 50%                                            No. sition for 7 days 23° C.                                           relative humidity for 7 days                      ______________________________________                                         85      8      29            39                                                  86  9 -- 40                                                                    87 10 26 --                                                                    88 11 -- 50                                                                    89 I 14  9                                                                     90 16 41 130                                                                   91 III 14 11                                                                   92 IX 41 169                                                                   93 XII 110  171                                                                94 XI 87 127                                                                   95 VI  8  9                                                                    96 VII  45                                                                     97 VIII  34                                                                    98 XIII -- 11                                                                  99 XIV --  9                                                                   100  XV --  9                                                                  101  18 19 182                                                                 102  V  8  7                                                                   103  XVI  2 22                                                                 104  XX 57 241                                                                 105  XVIII -- 22                                                               106  XXI 12 22                                                                 107  XIX -- 46                                                                 108  XXII -- 51                                                                109  XXIII -- 14                                                               110  XXIV -- 13                                                                111  XXV --  8                                                               ______________________________________                                          1. Film had craters.                                                     

112-115. Mar Resistance. The compositions of the present invention have improved mar resistance when cast as films. The mar resistance was measured using an AATCC crockmeter, Atlas Electric Devices Company, model CM-5. Films were cast into Bonderite treated cold-rolled steel panels using a draw down bar and cured at 121° C. for 20 minutes and 23° C. and 50% relative humidity for seven days. The gloss values were determined according to ASTM D 523. The results of the mar resistance of these films are reported in Table IV. Films cast from compositions of the present invention demonstrated an improvement in mar resistance for compositions freshly prepared and aged 6 months (Examples 112 and 113) as compared to compositions from Comparative Examples XLIV and IV (Examples 114 and 115).

                  TABLE IV                                                         ______________________________________                                         Data showing that the mar resistance of films                                    cast from compositions of present inventions are better                        than simple mixture of epoxy silane and acid modified polymers                                                Gloss after                                     Example No. Composition Initial Gloss (60                                                                             °) 10 cycles % loss            ______________________________________                                         112     14.sup.1    96         32      67                                        113 14.sup.2 100 50 50                                                         114 XLIV  98 26 73                                                             115 IV 103 24 77                                                             ______________________________________                                          .sup.1 film cast immediately after preparation of composition                  .sup.2 film cast 6 months after preparation of composition.              

116-125. Hardness--Films cast from the compositions of the present invention had an increase in hardness while maintaining other film properties, such as gloss, and adhesion, as indicated in Table V. Pencil hardness was measured according to ASTM D 3363-74. The gloss was measured according to ASTM-D 523. Crosscut tape adhesion was measured according to ASTM 3359-90. Wet adhesion of the film to E-coat steel panel was measured according to Method 6301 of US Federal Standard Test Method 141B. The films were prepared using a draw down bow. The dry film thickness was 2 mils. The films were cured at 121° C. for 20 minutes and 23° C. and 50% relative humidity for 7 days.

                  TABLE V                                                          ______________________________________                                         Data showing that composition of present invention                               give a good balance of film properties after curing at                         121° C. for 2 minutes and 23° for 7 days                                    Gloss                                                               value Hardness Tape Wet                                                      Example                                                                               Composition                                                                              20°                                                                           60°                                                                          Pencil Adhesion                                                                              Adhesion                             ______________________________________                                         116    16        84     97  HB     5B     10                                     117 17 78  99 H 5B 10                                                          118 XII 64  92 F 5B 10                                                         119 VI 80  99 B 5B 10                                                          120 III 89 105 B 5B 10                                                         121 18 80  94 2H 5B 10                                                         122 19 64  92 F 5B 10                                                          123 XX 80  99 HB 5B 10                                                         124 XXI 80  99 HB 5B 10                                                        125 V 96 107 B 5B 10                                                         ______________________________________                                    

A dramatic illustration of the usefulness of the composition of the present invention is presented for a filled latex sealant. The sealant formulations are set forth in Table VI. The sealants were prepared by charging UCAR latex polymer 105 and TRITON X-405 into a mixing vessel and stirring for five minutes. A solution of NUOCEPT 95 preservative, TRITON X-405 surfactant and water was added to the mixing vessel and stirred for five minutes. The ethylene glycol, TEMOL 850 dispersing agent, ASE 60 thickener, KTPP potassium tripolyphosphate, and SANTICISER 160 plasticizer were added and mixed using a high speed mixing propeller. Mineral spirits, precursor epoxy silane emulsion or silicone additive and ammonium hydroxide were added and mixed using a spatula. A MOLTINI PLANAMAX mixer was used to stir the mixture for 20 minutes under a nitrogen atmosphere. The TiO₂ and DMDEE (2,2-dimorpholino diethyl ether) catalysts were added and mixed for five minutes. The mixture was degassed under reduced pressure for five minutes. The sealant was stored in a plastic sealant tube.

The sealants were cured at 23° C. and 50% relative humidity for three weeks in an environmental chamber and 1 week at ambient conditions. The physical properties of the cured sealants were measured according to ASTM D 412C (percent elongation, tensile strength and modulus), ASTM 624 (tear strength), C-661 (shore A hardness) and C-794 (adhesion in peel).

The sealants were heat aged at 50° C. for 4 weeks. The physical properties of the sealant are reported in Table VI. The compositions of the present invention, when fully formulated into a filled acrylic latex (Example 129), had excellent adhesion while maintaining high elongation and low modulus, especially after aging for 4 weeks at 50° C. The comparative examples 126-28, 130-31 had either poor adhesion after heat aging or dramatic loss of percent elongation.

                  TABLE VI                                                         ______________________________________                                         Data showing that the compositions of the present invention                      give a good balance of properties in a filled latex selant                                         LATEX SEALANT                                              FORMULATIONS                                                                 1. FILLED FORMULATION                                                            Components Parts Source                                                      ______________________________________                                         UCAR ® Latex Polymer 105                                                                         200.00  Union Carbide                                      TRITON ® X-405 (70% Active Surfactant) 3.45 Union Carbide                  NUOSEPT ® 95 (Preservative) 0.50 Huls                                      TRITON ® X-405 0.50 Union Carbide                                          Distilled Water 0.50                                                           Ethylene Glycol 4.95 Aldrich                                                   TEMOL ® 850 (Dispersing Agent) 0.50 Rohm & Haas                            ASE ® 60 (Thickener) 4.00 Rohm & Haas                                      KTPP (Potassium Tripolyphosphate) 0.50 FMC                                     SANTICISER ® 160 (Plasticizer) 50.00 Monsanto                              Mineral Spirits 4.00 Aldrich                                                   Organofunctional Silane or precursor 2.00 OSi Specialties                      epoxy emulsion                                                                 Ammonium Hydroxide (28% Soln) 1.00 Fisher                                      DRIKALITE ® (Treated Calcium Carbonate) 230.00 ECC                         Titanium Dioxide R-901 4.00 DuPont                                             DMDEE (Catalyst) 0.50 Texaco                                                 ______________________________________                                    

    __________________________________________________________________________     PHYSICAL PROPERTIES.sup.a FOR FILLED ACRYLIC                                     LATEX SEALANT FORMULATION                                                                                     Adhesion                                               to                                                                             Anodized Cohesive                                                         Elongation Tensile Modulus Tear Hardness Aluminum Failure                    Example Silane % (psi) (Young's) (lbs/in) (Shore A) (lbs/in) Mode            __________________________________________________________________________                                           (%)                                      126  None                                                                         Initial 400  44.8  43.3 19.7  6  8.1  65%                                      Aged.sup.b 347  41.2  29.0 20.1 15  9.5  10                                   127 Z                                                                           Initial 287  62.4  39.3 22.9 20  7.2  95%                                      Aged 158 110.6 119.4 30.1 15  5.8  98%                                        128 A                                                                           Initial 300  72.6  36.2 26.6 23  4.4 100%                                      Aged  70 116.3 313.8 16.4 16  3.4 100%                                        129 Example 1                                                                   Initial 300  73.3  41 36.5 15  7.7  93%                                        Aged 199  82.5  60.6 29.1 22 11.2  90%                                        130 W                                                                           Initial 567  27.4  9.3  9.3 15  5.1  20%                                       Aged 200 125.3  25.5 25.5 24  7.5  7%                                         131 T                                                                           Initial 253  53.2  26.9 26.9 28  9.1 100%                                      Aged 219  39.1  20.2 20.2 21  8.0  20%                                      __________________________________________________________________________      .sup.a Physical properties measurements obtained in accordance with            accepted ASTM test specifications; .sup.b Samples were aged for four (4)       weeks at 50° C.;                                                        A = (3,4epoxycyclohexyl)ethyltriethoxysilane                                   T = 3aminopropylsiloxanes in water                                             Z = 3glycidoxypropyltrimethoxysilane                                           Example 1. Precursor epoxy silane emulsion prepared in Example 1               W = amyltriethoxysilane. (The silane was added as an emulsion prepared by      mixing 40 grams of amyltriethoxysiloxane, 4.11 grams of SPAN60 and 3.87        grams of TWEEN 40 and 52 grams of water.)                                

EXAMPLES USING AMINE CATALYSTS

The following examples demonstrate the very satisfactory and superior results obtained when an amine catalyst is present in the composition, in accordance with the present invention.

The tests were carried out using either a commercially available styrene acrylic latex sealer/topcoat with an acid number of 10.7, termed "Latex X" hereinafter, or "Rhoplex CL-204" (Rohm & Haas), both of which are commercial acrylic latexes with pendant carboxylic groups.

In each test, the components indicated were combined, the resulting composition was cured, and the properties of the cured product were determined 4 hours, 3 days, and 7 days later. The test procedures were as described hereinabove.

Amine catalysts identified by product name are:

    ______________________________________                                         Anquamide 360 (Air Products)                                                                    Polyethylene polyamine, polyamide                                solution                                                                      Anquamine 401 (Air Products) Tetraethylene pentamine                           EMI-24 (Air Products) 2-Ethyl-4-methyl-1H-                                      imidazole                                                                     DMP-30 and DY-064 (Ciba, Tris-2,4,6-(dimethylamino-                            now Novartis) methyl)phenol                                                    BMDA and DY-062 (Ciba, N-Benzyl-N-dimethylamine                                now Novartis)                                                                  PE-1013 (ELF Atochem) Dibutyltin bis(1-thioglycerol)                         ______________________________________                                    

Sample Description: Latex X+1% [14.89% Anquamide 360/water]+3% of 40% emulsion of Silane "Y-1" (β-[3,4-epoxycyclohexyl]-ethyl triethoxysilane)

    ______________________________________                                         SAMPLES                    pH                                                  ______________________________________                                           Latex X 6.78                                                                   14.89% Anquamide 360/water. 9.33                                               Latex X + 1% of [14.89% Anquamide 360/Water]. 7.9                              Latex X + 1% of [4.89% 7.81                                                    Anquamide 360/water + 3% of 40% Y-1 emulsion.                                  1% of 14.89% Anquamide 360/water was added with                                1.74% Dowanol PnB to Latex X [No gel                                           particles were present]                                                      ______________________________________                                         CURING CYCLE FOR COATED PANELS 15 min.                                           baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           at 50° C. for 2 hr. 2 lb 2 8 9                                           4 lb 2 8 7                                                                    At Room 2 lb 10 10 10                                                          Temp. [4 hr.] 4 lb 10 10 10                                                    Pencil Hardness  2B HB B                                                       Methyl Ethyl Ketone  31 76 181                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.3 1.8 1.9                                       ______________________________________                                    

Sample Description: Latex X+1% [28.89% Anquamine 401/water]+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES              pH                                                        ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% Anquamine 401 8.47                                                Latex X + 1% Anquamine 401 + 8.55                                              3% of 40% Y-1 emulsion                                                       ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for :                                                             CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for 2 2 lb. 5 9 9                                             hr.                                                                             4 lb. 2 9 7                                                                   At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 10 10 10                                                   Pencil Hardness  HB HB HB                                                      Methyl Ethyl  21 61 >400                                                       Ketone                                                                         Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.8 1.9                                       ______________________________________                                    

Sample Description: Latex X+1% EMI-24+3% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES             pH                                                         ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% EMI-24 8.97                                                       Latex X+ 1% EMI-24 + 3% 8.91                                                   of 40% Y-1 emulsion                                                          ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 6 9 9                                        4 lb. 3 8 9                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  2B F F                                                        Methyl Ethyl Ketone  72 241 >400                                               Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.3 1.8 1.9                                       ______________________________________                                    

Sample Description: Latex X+1% Ethyltriphenylphosphinium Bromide+3% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES                    pH                                                  ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% Ethyltriphenylphosphonium Bromide 6.48                            Latex X + 1% Ethyltriphenylphosphonium Bromide + 6.51                          3% of 40% Y-1 emulsion.                                                      ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                               CURING TIME AT                                               AMBIENT TEMP.                                                                                        .17 day 3 days 7 days                                  ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 7 7 7                                        4 lb. 7 7 7                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 9 10 10                                                                 Pencil Hardness  3B B 2B                                                       Methyl Ethyl Ketone                                                            Resistance Test [Double Rubs]  38 56 171                                       Coating Thickness [mils.]  1.7 1.5 1.8                                       ______________________________________                                    

Sample Description: Latex X+1% DMP-30+% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES               pH                                                       ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% DMP-30 9.65                                                       Latex X + 1% DMP-30 + 3% of 40% 9.6                                            Y-1 emulsion.                                                                ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 7 5 5                                        4 lb. 3 3 3                                                                   At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 9 10 10                                                    Pencil Hardness  3B 2B 3B                                                      Methyl Ethyl Ketone  32 78 128                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.9 1.05 1.8                                      ______________________________________                                    

Sample Description: Latex X+1% BMDA+3% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES            pH                                                          ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% BMDA 8.69                                                         Latex X + 1% BMDA + 8.69                                                       3% of 40% Y-1 emulsion.                                                      ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 6 7 5                                        4 lb. 3 7 7                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  3B B B                                                        Methyl Ethyl Ketone  26 78 102                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.6 1.9 1.9                                       ______________________________________                                    

Sample Description: Latex X+1% (Butyl) triphenylphosphonium Bromide+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                    pH                                                  ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% (Butyl)triphenylphosphonium Bromide 8.38                          Latex X + 1% (Butyl)triphenylphosphonium 6.44                                  Bromide + 3% of 40% Y-1 emulsion                                             ______________________________________                                         CURING CYCLE FOR COATED PANELS                                                   15 min. baked @ 150° F., Cured for:                                                      CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day  3 days                                                                               7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 4 7 8                                        4 lb. 3 7 8                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 9 10 10                                                                 Pencil Hardness  3B 2B B                                                       Methyl Ethyl Ketone                                                            Resistance Test [Double Rubs]  38 140 157                                      Coating Thickness [mils.]  1.8 1.9 1.8                                       ______________________________________                                    

Sample Description: Latex X+1% Benyltrimethylammonium Chloride+3% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES                   pH                                                   ______________________________________                                           Latex X 6.78                                                                   Latex X + 1% Benzyltrimethylammonium Chloride 6.49                             Latex X + 1% Benzyltrimethylammonium 6.52                                      Chloride + 3% of 40% Y-1 emulsion                                            ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min. baked                                    @ 150° F., Cured for:                                                                    CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day  3 days                                                                               7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 4 7 7                                        4 lb. 1 5 5                                                                   At Room Temp. [4 hr.] 2 lb. 9 10 10                                             4 lb. 8 10 10                                                                 Pencil Hardness  >5B 4B 2B                                                     Methyl Ethyl Ketone  25 28 29                                                  Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.8 2 1.7                                         ______________________________________                                    

Sample Description: Latex X+0.2% Tin [II] Chloride+3% of 40% Y-1 emulsion.

    ______________________________________                                         SAMPLES                      pH                                                ______________________________________                                           Latex X 6.68                                                                   Latex X + 0.2% Tin [II] Chloride. 3.89                                         Latex X + 0.2% Tin [II] Chloride + 3% of 40% Y-1 emulsion 3.95               ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day  3 days                                                                               7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 7 6 6                                        4 lb. 3 3 5                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B HB HB                                                       Methyl Ethyl Ketone  38 35 43                                                  Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.8 1.3 1.1                                       ______________________________________                                    

Sample Description: Latex X+1% of 50% Accelerator DY 062/water+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                      pH                                                ______________________________________                                           Latex X 6.78                                                                   50% Accelerator DY-062/water [Insoluble] 10.9                                  50% Accelerator DY-062/water + 20% Acetic acid [Soluble]. 7.45                 Latex X + 1% of 50% Accelerator DY 062/water/Acetic acid 6.43                  Latex X + 1% of 50% Accelerator DY 062/water/Acetic 6.5                        acid + 3% of 40% Y-1 emulsion                                                ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                       CURING TIME                                                                        .17      3    7                                            day days days                                                              ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 4 5 6                                        4 lb. 4 1 5                                                                   At Room Temp. [4 hr.] 2 lb. 9 10 10                                             4 lb. 9 10 10                                                                 Pencil Hardness  2B 2B B                                                       Methyl Ethyl Ketone  49 52 72                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.8 1.3 1.6                                       ______________________________________                                    

Sample Description: Latex X+1% of 25% Fomrez UL-22 emulsion+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                    pH                                                  ______________________________________                                           Latex X 6.78                                                                   25% Fomrez UL-22 emulsion [25% Fomrez UL-22 +                                  35.5%                                                                          Igepal CA-897 (Non Ionic surfactant) + 39.5% water. 6.23                       Latex X + 1% of 25% Fomrez UL-22 emulsion. 6.84                                Latex X + 1% of 25% Fomrez UL-22 emulsion + 6.75                               3% of 40% Y-1 emulsion                                                       ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                        CURING TIME                                                                        .17     3     7                                         day days days                                                                ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 4 7 8                                        4 lb. 2 3 6                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  3B 2B B                                                       Methyl Ethyl Ketone  59 114 130                                                Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.9 1.7 1.7                                       ______________________________________                                    

Sample Description: Latex X+1% of 25% PE-1013 [Tin catalyst] emulsion+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                 pH                                                     ______________________________________                                           Latex X 6.78                                                                   25% PE-1013 emulsion [25% PE-1013 (Tin 6.61                                    catalyst) + 35.5% Igepal CA-897 (non Ionic                                     surfactant) + 39.5% water.                                                     Latex X + 1% of 25% PE-1013 emulsion. 6.86                                     Latex X + 1% of 25% PE-1013 emulsion + 6.86                                    3% of 40% Y-1 emulsion                                                       ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 2 5 5                                        4 lb. 2 2 4                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 9 10 10                                                                 Pencil Hardness  2B 2B B                                                       Methyl Ethyl Ketone  65 69 278                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.8 1.5 2.1                                       ______________________________________                                    

Sample Description: Latex X+0.5% Dowanol

    ______________________________________                                         SAMPLES              pH                                                        ______________________________________                                           Latex X + 0.5% Dowanol PnB. 6.78                                             ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 9 10 10                                      4 lb. 9 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  HB B HB                                                       Methyl Ethyl Ketone  28 27 28                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.1 1.3 1.7                                       ______________________________________                                    

Sample Description: Latex X+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES               pH                                                       ______________________________________                                           Latex X 6.78                                                                   Latex X + 3% of 40% Y-1 emulsion. 6.94                                       ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 5 5 10                                       4 lb. 1 1 9                                                                   At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 9 10 10                                                    Pencil Hardness  2B 2B F                                                       Methyl Ethyl Ketone  32 40 46                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.7 1.4 1.2                                       ______________________________________                                    

Sample Description: Latex X+1% DY 064 [catalyst]+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                  pH                                                    ______________________________________                                           Latex X 6.68                                                                   Latex X + 1% DY 064 [catalyst]. 9.48                                           Latex + 1% DY 064 + 3% of 40% Y-1 emulsion. 9.39                             ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                       CURING TIME                                                                        .17 day 3 days 7 days                                  ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 6 5 3                                        4 lb. 1 1 2                                                                   At Room Temp. [4 hr.] 2 lb. 9 10 10                                             4 lb. 9 10 10                                                                 Pencil Hardness  2B 2B HB                                                      Methyl Ethyl Ketone  51 53 78                                                  Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.63 1.7 1.9                                      ______________________________________                                    

Sample Description: Latex X+1% of 20% DY 9577/Dowanol PnB+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                  pH                                                    ______________________________________                                           Latex X 6.68                                                                   Latex X + 1% of 20% DY 9577/Dowanol PnB. 6.59                                  Latex X + 1% of 20% DY 9577/Dowanol PnB + 6.66                                 3% of 40% Y-1 emulsion                                                       ______________________________________                                         CURING CYCLE: 15 min. baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 5 5 3                                        4 lb. 1 1 1                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  2B 2B HB                                                      Methyl Ethyl Ketone  28 28 27                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.4 1.6 1.3                                       ______________________________________                                    

Sample Description: Latex X+1% of 65% Dibutyl Tin Oxide Dispersion+3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                   pH                                                   ______________________________________                                           Latex X 6.68                                                                   65% Dibutyl Tin Oxide Dispersion [lot #52- 9.22                                4)                                                                             Latex X + 1% of 65% Dibutyl Tin Oxide Dispersion 6.89                          Latex X + 1% of 65% Dibutyl Tin Oxide 7.16                                     Dispersion + 3% of 40% Y-1 emulsion                                          ______________________________________                                         CURING CYCLE: 15 min baked                                                       @ 150° F., Cured for:                                                                     CURING TIME                                                                        .17 day 3 days 7 days                                  ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 5 8 9                                        4 lb. 3 6 8                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  2B HB HB                                                      Methyl Ethyl Ketone                                                            Resistance Test [Double Rubs]  66 160 160                                      Coating Thickness [mils.]  1.5 1.5 1.8                                       ______________________________________                                    

Sample Description: Rhoplex CL--204, Formulation WR--204--2 [no

    ______________________________________                                                SAMPLES    pH                                                           ______________________________________                                           Rhoplex CL 204 6.72                                                            Rhoplex WR-204-2 8.1                                                           [Formulated]                                                                 ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME                                                   AT AMBIENT TEMP.                                                                                    .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          at 50° C. for 2 hr. 2 lb 10 10 10                                        4 lb 10 10 10                                                                 AT Room Temp. [4 hr.] 2 lb 10 10 10                                             4 lb 10 10 10                                                                 Pencil Hardness  2B B 2B                                                       Methyl Ethyl Ketone  19 17 19                                                  Resistance Test                                                                [Double Rubs]                                                                  Coating Thickness [mils.]  2.8 1.7 2.8                                       ______________________________________                                    

Sample Description: Rhoplex CL--204, Formulation WR--204--2+3% of 40% emulsion of silane "Y-2" [2-(3,4-Epoxycyclohexyl)ethyltriethoxy

    ______________________________________                                         SAMPLES              pH                                                        ______________________________________                                           Rhoplex CL 204 6.72                                                            Rhoplex WR-204-2 [Formulated] 8.1                                              Rhoplex WR-204-2 + 3% Y- 8.13                                                  2 emulsion                                                                   ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for 2 hr. 2 lb. 10 9 10                                        4 lb. 9 9 10                                                                  At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 10 10 10                                                   Pencil Hardness  B B B                                                         Methyl Ethyl  33 30 149                                                        Ketone                                                                         Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.9 1.4                                       ______________________________________                                    

Sample Description: Rhoplex CL 204,Formulation 204--2+1% Benyltrimethylammonium Chloride+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                       pH                                               ______________________________________                                           Rhoplex CL 204 6.72                                                            Rhoplex WR 204-2 8.1                                                           Rhoplex WR 204-2 + 1% Benzyltrimethylammonium Chloride 8.2                     Rhoplex WR 204-2 + 1% Benzyltrimethylammonium Chloride + 8.35                  3% of 40% Y-2 emulsion                                                       ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C for [2 hr.] 2 lb. 8 8 9                                         4 lb. 7 7 8                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 8 0 10                                                                  Pencil Hardness  >5B 3B 2B                                                     Methyl Ethyl Ketone  23 29 32                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.7 1.9                                       ______________________________________                                    

Sample Description: Rhoplex CL-204,Formulation 204--2+0.4% (Ethyl)triphenylphosphonium Bromide+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                        pH                                              ______________________________________                                           Rhoplex WR 204-2 8.1                                                           Rhoplex WR-204-2 + 0.4% (Ethyl)triphenylphosphonium 8.4                        Bromide                                                                        [5% (Ethyl)triphenylphosphonium Bromide + 81.94% water + 1.85%                 Arcosolve DPTB, + 3.71% Arcosolve DPM and 7.5% Butyl                           Propasol.]                                                                     Rhoplex WR-204-2 + .4%(Ethyl) triphenylphosphonium 8.5                         Bromide                                                                        [5% (Ethyl)triphenylphosphonium Bromide + 81.94% water +                       1.85% Arcosolve DPTB, 3.71% Arcosolve DPM and 7.5% Butyl                       Propasol] + 3% of 40% Y-2 emulsion                                           ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                               CURING TIME AT                                               AMBIENT TEMP.                                                                                        .17 day 3 days 7 days                                  ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 9 10 10                                      4 lb. 8 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B B B                                                         Methyl Ethyl Ketone  24 70 24                                                  Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.8 1.5 1.6                                       ______________________________________                                    

Sample Description: Rhoplex CL 204, Formulation WR 204--2+1% EMI--24 [15% EMI--24/Water]+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES              pH                                                        ______________________________________                                           Rhoplex WR 204-2 8.1                                                           Rhoplex WR 204-2 + 1% EMI-24 8.75                                              [15% EMI-24]                                                                   Rhoplex WR-204-2 + 1% 8.86                                                     EMI-24 + 3% of 40% Y-2                                                         emulsion                                                                     ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                             PANELS:                                                                                         CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 9 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B B B                                                         Methyl Ethyl Ketone  21 219 >400                                               Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.6 1.6                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% N-Benzyl-N-Dimethylamine (BMDA) [50% BMDA, 3.7% Arcosolve DPTB, 7.4% Arcosolve DPM and 38.9% Butyl Propasol]+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                     pH                                                 ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex WR-204-2 + 1% N-Benzyl-N- 8.9                                          Dimethylamine [BMDA]                                                           [50% BMDA, 3.7% Arcosolve DPTB, 7.4% Arcosolve                                 DPM, and 38.9% Butyl Propasol]                                                 Rhoplex WR-204-2 + 1% N-Benzyl-N- 8.9                                          Dimethylamine [BMDA]                                                           [50% BMDA, 3.7% Arcosolve DPTB, 7.4% Arcosolve                                 DPM and 38.9% Butyl Propasol] + 3% of 40% Y-2                                  emulsion                                                                     ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 9 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B HB HB                                                       Methyl Ethyl Ketone  26 68 192                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.9 1.9 1.7                                       ______________________________________                                    

Sample Description: Rhoplex CL--204 (Unformulated Resin)+0.4% (Butyl)--triphenylphosphonium Bromide [2.66% Butyltriphenylphosphonium Bromide, 24.75% Arcosolve DPM, 12.34% Arcosolve DPTB, 50.05% Butyl Propasol and 10.2% Water]+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                    pH                                                  ______________________________________                                         Rhoplex CL-                6.78                                                  204 (unformulated) 8.5                                                         Rhoplex CL-204 (Unformulated, pH                                               adjusted to 8.5 with 14% Ammonium                                              Hydroxide solution.)                                                           Rhoplex CL-204 [pH 8.5, Unformulated] + 7.9                                    0.4% (Butyl)-triphenylphosphinium                                              Bromide [2.66% (Butyl)triphenylphosphonium Bromide]                            Rhoplex CL-204 [pH 8.5, Unformulated] + 8.01                                   0.4% (Butyl)-triphenylphosphinium                                              Bromide [2.66% (Butyl)triphenylphosphonium Bromide] +                          3% of 40% Y-2 emulsion                                                       ______________________________________                                    

Sample Description: Rhoplex CL-204 (Unformulated resin)+0.4% (Butyl-triphenylphosphonium Bromide [2.66% Butyltriphenyl phosphomium Bromide, 24.75% Arcosolve DPM, 12.34 Arcosolve DPTB, 50.05% Butyl Propasol and 10.2% Water]+3% of 40% Y-2 emulsion

    ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 2 9 6                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B HB B                                                        Methyl Ethyl Ketone  48 48 231                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.7 1.9 1.3                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% of 9.49% Anquamide 360 [Anquamide 9.49%, Arcosolve DPTB, 18% Butyl Propasol 68.91%, Water 4.59%]+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                  pH                                                    ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex WR-204-2 + 1% of Anquamide 360 8.2                                     [Anquamide 9.49%, Arcosolve DPTB                                               18%, Butyl Propasol 68.91%, Water                                              4.59%]                                                                         Rhoplex WR-204-2 + 1% of Anquamide 8.26                                        360 + 3% of 40% Y-2 emulsion                                                 ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 9 10 10                                      4 lb. 5 9 9                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  F F F                                                         Methyl Ethyl Ketone  18 31 139                                                 Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.6 1.7 1.6                                       ______________________________________                                    

Sample Description: Rhoplex CL--204--2+1% of a 20% formulation of silane "Y-3" {1-[3-(trimethoxysilyl) propyl]-1H-Imidazole} (The emulsion consisted of {20% silane Y-3, Ethanol 200 proof 53.3%, Distilled water 17.78%, Glacial Acetic acid 8.89%. The pH of the mixture was adjusted to 8.5-9.0 with conc. Ammonium Hydroxide]+3% of a 40% emulsion of silane Y-2.

    ______________________________________                                         SAMPLES                   pH                                                   ______________________________________                                           Rhoplex CL-204-2 8.1                                                           Rhoplex CL-204-2 + 1% of a 20% formulation of 8.3                              silane Y-2                                                                     Rhoplex CL-204-2 + 1% of a 20% 8.3                                             formulation of silane Y-3 + 3% of a                                            40% emulsion of silane Y-2                                                   ______________________________________                                         CURING CYCLE FOR COATED PANELS: 15 min.                                          baked @ 150° F., Cured for:                                                              CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 10 10 10                                                                At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  2B B F                                                        Methyl Ethyl Ketone  72 219 >400                                               Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.6 1.9                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% of the 20% formulation of Y-3+3% of the 40% emulsion of silane Y-2

    ______________________________________                                         SAMPLES                   pH                                                   ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex WR-204-2 + 1% of 20% formulation of 8.3                                Y-3                                                                            Rhoplex WR-204-2 + 1% of 20% formulation of 8.3                                Y-3 + 3% of 40% emulsion of Y-2                                              ______________________________________                                         CURING CYCLE FOR COATED PANELS: [Non Baked]                                      @ Ambient Temp., Cured for:                                                                     CURING TIME AT                                                AMBIENT TEMP.                                                                                       .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance Test                                                          At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 9 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  B B F                                                         Methyl Ethyl Ketone  28 52 >400                                                Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.3 1.4                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% Anquamine-401 [15% Anquamine] and 85% water]+3% of 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                     pH                                                 ______________________________________                                           Rhoplex WR-204-2 8.2                                                           Rhoplex WR-204-2 + 1% Anquamine-401 8.6                                        [15% Anquamine-40 and 85% water]                                               Rhoplex WR-204-2 + 1% Anquamine-401 8.76                                       [15% Anquamine and 85% water] + 3% of 40% Y-2 emulsion                       ______________________________________                                         CURING CYCLE FOR COATED PANELS : 15 min.                                         baked @ 150° F., Cured for:                                                               CURING TIME AT                                               AMBIENT TEMP.                                                                                        .17 day 3 days 7 day                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 10 10 10                                     4 lb. 6 10 10                                                                 At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  F F F                                                         Methyl Ethyl Keytone  27 28 142                                                Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.8 1.7 1.8                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% EMI [50% EMI+25% Ethanol+25% water] and 3% of 40% Y-1 emulsion

    ______________________________________                                         SAMPLES                       pH                                               ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex WR-204-2 + 1% EMI [50% EMI + 25% Ethanol + 25 8.2                      % water]                                                                       Rhoplex WR-204-2 + 1% EMI [50 8.2                                              % EMI + 25% Ethanol + 25% water)                                               and 3% Y-1 emulsion]                                                         ______________________________________                                         CURING CYCLE : 15 min. baked @ 150° F.,                                   Cured for:                                                                                    CURING TIME                                                                        .17 day   3 days                                                                               7 days                                    ______________________________________                                           Print Resistance                                                               Test                                                                           At 50° C. for [2 hr.] 2 lb. 9 10 10                                      4 lb. 9 9 10                                                                  At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  2B 2B HB                                                      Methyl Ethyl Ketone                                                            Resistance Test [Double  62 73 >400                                            Rubs]                                                                          Coating Thickness [mils.]  1.7 1.2 1.6                                       ______________________________________                                    

Sample Description: Rhoplex WR--204--2+1% EMI [50% EMI+25% Ethanol+25% water] and 3% of 40% Y-1

    ______________________________________                                         SAMPLES                       pH                                               ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex WR-204-2 + 1% EMI [50% EMI + 25% Ethanol + 25 8.2                      % water]                                                                       Rhoplex WR-204-2 + 1% EMI [50% EMI + 25% Ethanol + 25 8.2                      % water] and 3% Y-1 emulsion                                                 ______________________________________                                         CURING CYCLE : Non baked @ Room Temperature,                                     Cured for:                                                                                       CURING TIME                                                                        .17 day 3 days 7 days                                  ______________________________________                                           Print Resistance Test                                                          At 500 C. for [2 hr.] 2 lb. 9 10 10                                             4 lb. 8 9 10                                                                  At Room Temp. [4hr.] 2 lb. 10 10 10                                             4 lb. 10 10 10                                                                Pencil Hardness  3B 3B B                                                       Methyl Ethyl Ketone  37 45 >400                                                Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.3 1.7 1.3                                       ______________________________________                                    

Sample Description: Rhoplex CL--204--2+1% silane Y-3

    ______________________________________                                         SAMPLES            pH                                                          ______________________________________                                           Rhoplex WR-204-2 8.1                                                           Rhoplex CL-204-2 + 1% 8.3                                                      Silane Y-1                                                                   ______________________________________                                         CURING CYCLE: 15 mins. baked @ 150° F.,                                   Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 500 C. for [2 hr.] 2 lb. 6 10 10                                             4 lb. 3 10 10                                                                 At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 10 10 10                                                   Pencil Hardness  3B 2B 2B                                                      Methyl Ethyl Ketone  20 20 19                                                  Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.5 1.2 1.5                                       ______________________________________                                    

Sample Description: Latex X+1% of the 20% formulation of Y-3+3% of the 40% emulsion of Y-2

    ______________________________________                                         SAMPLES                 pH                                                     ______________________________________                                           Latex X 6.61                                                                   Latex X + 1% of 20% Y-3 formulation 6.13                                       Latex X + 1% of 20% Y-3 formulation + 3% 6.13                                  of 40% Y-2 emulsion.                                                         ______________________________________                                         CURING CYCLE: 15 mins baked @ 150° F.,                                    Cured for:                                                                                      CURING TIME                                                                        .17 day 3 days 7 days                                   ______________________________________                                           Print Resistance                                                               Test                                                                           At 500 C. for [2 hr.] 2 lb. 7 7 7                                               4 lb. 5 5 9                                                                   At Room 2 lb. 10 10 10                                                         Temp. [4 hr.] 4 lb. 10 10 10                                                   Pencil Hardness  3B HB HB                                                      Methyl Ethyl Ketone  32 55 >400                                                Resistance Test [Double                                                        Rubs]                                                                          Coating Thickness [mils.]  1.6 1.2 1.5                                       ______________________________________                                    

Sample Description: Latex X+1% of the 20% formulation of Y-3+3% of the 40% Y-2 emulsion

    ______________________________________                                         SAMPLES                pH                                                      ______________________________________                                           Latex X 6.61                                                                   Latex X + 1% of 20% Y-3 formulation 6.13                                       Latex X + 1% of 20% Y-3 formu- 6.13                                            lation + 3% of 40% Y-2 emulsion                                              ______________________________________                                         CURING CYCLE : Non                                                               baked @ Room Temperature, Cured for:                                                              CURING TIME                                                                        .17    3                                                  day days 7 days                                                            ______________________________________                                           Print Resistance                                                               Test                                                                           At 500 C. for [2 hr.] 2 lb. 7 8 7                                               4 lb. 5 7 7                                                                   At Room Temp. [4 hr.] 2 lb. 10 10 10                                            4 lb. 10 10 10                                                                Pencil Hardness  3B HB HB                                                      Methyl Ethyl Ketone  30 51 >400                                                Resistance Test [Double Rubs]                                                  Coating Thickness [mils.]  1.4 1.6 1.7                                       ______________________________________                                     

We claim:
 1. A composition comprising: (a) 0.1 to 20 weight percent of a water insoluble or slightly soluble epoxysilane; (b) 10 to 80 weight percent of water; (c) 25 to 60 weight percent of a polymer with pendant carboxylic acid groups; and (d) 0.1 to 20 weight percent of a tertiary amine catalyst wherein the epoxy silane is selected from the group consisting of: ##STR4## where: R is (CH₂)_(m), where m has a value of zero to six;R² is an alkyl, alkoxy-substituted allyl, aryl or aralkyl group, each of said groups having from one to ten carbon atoms; R³ is an alkyl, alkoxy-substituted alkyl, aryl or aralkyl group, each of said groups having from two to ten carbon atoms; and n has a value of zero, one or two.
 2. A composition according to claim 1 which is an emulsion and comprises an emulsifier.
 3. A composition according to claim 2 wherein the emulsifier is selected from the group consisting of: polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid salts, alkyl sulfate ester salts, alkyl benzene sulfonate, alkyl phosphate, alkylallyl, sulfate ester salt, polyoxyethylene alkylphosphate ester, quaternary ammonium salts, alkyl trimethylammonium salts, alkyl benzyl dimethyl ammonium salts, and dialkyl dimethyl ammonium salts.
 4. A composition according to claim 1 wherein the catalyst comprises N-benzyl-N-dimethylamine.
 5. A composition according to claim 1 wherein the catalyst comprises tris-2,4,6-(dimethylaminomethyl)phenol).
 6. A composition according to claim 1 wherein the catalyst comprises tetraethylenepentamine.
 7. A coating made from a composition according to claim
 1. 8. A composition according to claim 1 additionally comprising a pH buffer.
 9. The composition of claim 1 wherein the tertiary amine has a nittrogen atom substituted with three substituents selected from the group consisting of alkyl containing 1 to 6 carbons atoms, unsubstituted benzyl, benzyl substituted with one or more alkyl containing 1 to 6 carbon atoms or hydroxyl and dialkylaminoalkylene wherein each alkyl contains 1 to 6 carbon atoms and the alkylene bridge contains 1 to 6 carbon atoms.
 10. The composition of claim 9 wherein the tertiary amine is substituted with three alkyl groups of 1 to 6 carbon atoms.
 11. The composition of claim 9 wherein the tertiary amine is substituted with an unsubstituted benzyl group.
 12. The composition of claim 9 wherein the tertiary amine is substituted with a dialkylaminoalkylene group wherein alkyl contains 1 to 6 carbon atoms and the alkylene bridge contains 1 to 6 carbon atoms.
 13. The composition of claim 9 wherein the tertiary amine is substituted with a benzyl substituted with one or more alkyl containing 1 to 6 carbon atoms or hydroxyl. 